Process for the single-bath dyeing of unmodified polyolefin fibers with metal complex dyestuffs

ABSTRACT

Process for the single-bath dyeing or printing of unmodified polyolefin fibers with metal-complex dyestuffs, by reacting under high-temperature dyeing conditions on these textile materials aqueous liquors or printing pastes containing water-soluble or dispersed metallizable dyestuffs and compounds yielding polyvalent heavy-metal ions in the presence of a dispersion system on the basis of polyglycol ethers.

von der Eltz et a1.

Hoechst Aktiengesellschaft, Frankfurt am Main, Germany Filed: Mar. 1, 1973 Appl. No.: 336,904

Assignee:

Foreign Application Priority Data Mar. 7. 1972 Germany 2210878 U.S. C1 8/30; 8/42 D; 8/42 R;

8/93 Int. Cl D06p 1/36 Field of Search 8/42 D, 30, 93, 42 R References Cited UNITED STATES PATENTS 7/1963 Skeuse 8/42 D [451 July 15, 1975 3,097,044 7/1963 Skeuse 8/42 D 3,362,781 1/1968 Jirou et al 8/42 D 3,515,506 6/1970 Straley et a1 8/42 D 3,556,709 1/1971 Jirou et a1 8/42 D FOREIGN PATENTS OR APPLICATIONS 43-18181 8/1968 Japan 8/42 D 43-4206 2/1968 Japan 8/42 D OTHER PUBLICATIONS Cook, Handbook of Polyolefin Fibres (1967) Merrow Publishing Co., Ltd. pp. 139-141.

Primary Examiner-Leland A. Sebastian Assistant Examiner-B. Hunt Attorney, Agent, or F irm-Curtis, Morris & Safford [57] ABSTRACT Process for the single-bath dyeing or printing of unmodified polyolefin fibers with metal-complex dyestuffs, by reacting under high-temperature dyeing conditions on these textile materials aqueous liquors or printing pastes containing water-s0lub1e or dispersed metallizable dyestuffs and compounds yielding polyvalent heavy-metal ions in the presence of a dispersion system on the basis of polyglycol ethers.

10 Claims, N0 Drawings PROCESS FOR THE SINGLE-BATH DYEING OF UNMODIFIED POLYOLEFIN FIBERS WITH METAL COMPLEX DYESTUFFS The present invention relates to a process for the single-bath dyeing f unmodified polyolefin fibers with metal complex dyestuffs.

It is known that unmodified polyolefin fibers, for example, polypropylene fibers, are, generally, difficult to dye by direct dyeing methods. Besides the immediate dyeing of the spinning mass in the melt with pigment dyestuffs, the dyeing of piece goods made of such fibers with aqueous suspensions of pigment dyestuffs and curable binding systems is described which form a correspondingly coloured film layer fast to washing on the fiber surface when being heated. Disperse dyes used for dyeing polyester fibers and other hydrophobic fibers, however, yield under comparable thermal conditions only very fair dyeings when being fixed the yield of which is unproportioned with respect to the amount of dyestuff used.

Various methods for the modification of the polyolefin material allow to improve the dye receptivity of the fiber considerably. For example, nitrogen-containing copolymers having a basic effect are introduced into the spinning melt of the fibrous ground substance of which the fibers consist and so anchored in the macromolecule. The fibers, so modified, then have affinity towards the anionic dyestuffs. Polypropylene can also be modified in such a manner that compounds of such metals which can form fast colour lakes with metallizable dyestuffs are incorporated into the mass or fiber. Thus, the fiber properties are influenced either by a metal-containing copolymer or by special aftertreatment operations of the finished, unmodified fibrous material before dyeing, for example, as described in German Auslegeschriften Nos. 1,297 577; 1,469 600 and 1,619 601. But each of these processes for the modification of polyolefins requires additional operational expenditure which makes the fiber more expensive and sometimes inadvertantly affects the physical properties of the fiber, for example, by reducing its stability and elasticity or by increasing its inflammability.

It was, now, found that unmodified polyolefin fibers, preferably polypropylene fibers, can be dyed or printed in a single bath operation with metal complex dyestuffs when allowing aqueous liquors or printing pastes containing water-soluble or dispersed, metallizable dyestuffs and compounds yielding polyvalent heavy-metal ions to act, under high-temperature dyeing conditions, on these textile materials in the presence of a dispersion system on the basis of polyglycol ethers.

The present invention is based on the observation that when using metallizable dyestuffs and metallizing agents in the same bath in the presence of a certain dispersion system the colour lake formed in the liquid is obtained in a particular colloidal state of dispersion in which it shows a technically useful affinity towards the unmodified polyolefin fiber under suitable thermal conditions. When respecting the conditions mentioned above, the dyeings or prints can be effected according to the process claimed using the exhaustion method, the pad-steaming method or a printing method together with steam fixation of the dyes. The exhaustion method requires temperatures within the range of from 120 to 135C, preferably about 130C, and a period of action of 40 to 70 minutes, preferably about 60 minutes; the

pad-steaming and the print steaming method require temperatures within the range of from C to C, preferably about 130C, and a period of action of from 10 to 40 minutes, preferably about 30 minutes. These temperatures suggested are, while maintaining a technical safety zone, below the range of temperature (from to C) at which the polyolefin (or polypropylene) fiber melts.

To perform the process of the invention it is essential that the metal-free dyestuff and the second component necessary for the formation of the colour lakes, the metallizing agent, are applied from a liquor, i.e. at the same time and according to the single-bath method, in order to enable the formation of the metal complex compound under determined conditions. Although the dyeing of metal-modified polypropylene fibers also leads to the formation of the colour lakes from the dyestuff and the metallizing agent contained in the fiber, this process can, at best, take place at the fiber surface, ie at the places where a metal ion is situated on the metal-modified fiber. As the metal is in these cases placed in the external layer of the fiber, the dyestuff can no longer be deposited in the internal part of the fiber.

In the process of the invention, the colour lake is, however, formed outside the fibers in the liquor. As those colour lakes are necessarily water-insoluble, a dispersion system is required which maintains the colour lake formed in a suitable state of dispersion allowing a diffusion into and, thus, an absorption of the metal complex dyestuff by the fiber. This dispersion system essentially consists of a nonionic auxiliary on the basis of alkyl or alkylaryl-polyglycol ethers or oxethylated fatty acid polyglycol esters, preferably a reaction product of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxide, which is combined in the exhaustion method with anionic protective colloids having a dispersing effect, preferably those on the basis of ligninsulfonic acid, and in the pad-steaming or printsteaming method with non-ionic protective colloids having a thickening effect, preferably a completely etherified locust bean flour.

Within the process of the invention it can be considered as surprising that these colour lake dispersions show affinity towards the unmodified polyolefin fibers in the presence of the said dispersing agents. It could not, either, be expected, that the oxethylation product mentioned considerably accelerated the formation of the colour lake.

The metallizable dyestuffs to be used for carrying out the dyeings according to the novel method may be watersoluble (mordant dyestuffs) or water-insoluble (metallizable disperse dyestuffs). Chemically spoken, these types of dyestuffs are compounds which form a coordinative complex with polyvalent metal atoms because of determined constitutional conditions, the metal being linked partially by a principal, partially by a secondary valency. These dyestuffs are products selected from different chemical classes of compounds. In this field, dyestuffs of different categories of compounds are suitable which contain an o-hydroxycarbonyl-group (for example o-hydroxyanthraquinones) or a o-hydroxycarboxyl-group (for example salicylic acid derivatives) or which contain in orthoor peri-position two hydroxyl groups or one hydroxy and one carboxyl group (for example alizarines). Furthermore, this class of dyestuffs comprises azo compounds which contain in orthoor peri-position to the azo group (-N=N-) in one or, better, in both of the aromatic nuclei a hydroxyl or carboxyl group or in the one nucleus a hydroxyl or carboxyl group and in the other nucleus of the azo dyestuff an amino group. Dyestuffs of the type disclosed above are described in detail in literature.

Suitable metallizing agents are, according to the invention, compounds of chromium, copper, iron, cobalt, nickel, zinc and aluminium which split off corresponding metal ions, especially under heat without having a negative influence on the bath stability, for example, by the formation of hydroxides, for example, salts of organic or inorganic acids, such as chelates relatively unstable under the action of heat of these metal ions forming colour lakes with nitriloacetates, ethylenediaminetetraacetates, polyphosphates, tartrates, citrates or with aliphatic amines, especially triethanol amine, or also with ammonia.

The mordant dyestuffs metallizable with chromium are especially important because of the fact that their colour lakes yield fat dyeings of pleasant shades.

Among the metallizing agents mentioned above the chromium (lIl)-acetato-sulfate used in accordance with the invention is of outstanding importance. It has the following formula:

Cr cH ,coo

cu coo cu coo EXAMPLE l:

Flock material of unmodified polypropylene fibers was dyed in a dyeing apparatus under high-temperature conditions, with a goods-to-liquor ratio of l 20, for 60 minutes at 130C with an aqueous liquid which contained, calculated on the weight of the dry material, the following components:

2 percent of the mordant dyestuff of the formula I COOH 2 percent of an anionic protective colloid on the basis of lignin-sulfonic acid 5 rinsed, soaped and dried in usual manner.

A brilliant orange dyeing was obtained the colour intensity of which was adequately related to the amount of dyestuff used.

EXAMPLE 2:

The dyeing was carried out in an analogous manner as described in Example 1, using, however 2 of the mordant dyestuff of the formula Ho 0 NH A brilliant, fast green dyeing was obtained.

EXAMPLE 3:

Dyeing was carried out in an analogous manner as described in Example 1, using, however,

2 percent of the mordant dyestuff of the formula no 5 OH A fast wine-red dyeing was obtained.

EXAMPLE 4:

Dyeing was carried out in an analogous manner as described in Example 1. The dyestuff used in this case was, however,

2 percent of the mordant dyestuff of the formula COOH COOH

A fast, blue dyeing was obtained.

EXAMPLE 5:

Dyeing was carried out as described in Example 1, using, however, an aqueous liquid of a dispersed azo pigment which was formed by diazotizing and coupling 1 percent of the aromatic primary amine 6-chloro-3- amino-indazole with the Azoic Coupling Component 12- C.I.No. 37.550 and containing as metallizing agent the following combination of chemicals:

1.6 percent of cobalt (IlI)-chloride-dihydrate,

8 percent of sodium-nitrilotriacetate,

1 percent of the reaction product of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxide and 5 percent of an anionic protective colloid on the basis of lignin-sulfonic acid.

The percentage numbers indicated above are calculated on the weight of the dry material.

After finishing, a fast green dyeing was obtained.

EXAMPLE 6:

Dyeing was carried out in an analogous manner as described in Example 5, but instead of the combination mentioned therein the following combination of metallizing agents was used:

1.2 percent of crystalline copper sulfate,

4 percent of triethanol amine,

1 percent of the reaction product of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxide and 5 percent of an anionic protective colloid on the basis of lignin-sulfonic acid. A fast grey dyeing was obtained.

EXAMPLE 7:

As described in Example 1, the fibrous material indicated therein was dyed while using, however,

2 percent of the disperse dye of the formula disclosed in German Auslegeschrift No. 1,619,601 in Example 9, and as metallizing agent the combination of 2 percent of aluminum sulfate (crystallized) A1,.

03- s 4 percent of a sequestring agent of the type of sodium polyphosphate, 1 percent of the reaction product of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxide and 5 percent of an anionic protective colloid on the basis of lignin-sulfonic acid. A brilliant fast red dyeing was obtained.

EXAMPLE 8:

A dyeing was prepared in an analogous manner as described in Example 1, using, however 2 percent of the disperse dye of the formula Ho '0' on" l HO O CHg-CHg-CHg-CHn described in German Auslegeschrift No. 1,619,601 in Example 12 and as metallizing agent a combination of 1 percent of nickel (ll)-sulfate-hexahydrate, 3 percent of sodium-nitrilotriacetate, 1 percent of the reaction product of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxide and 5 percent of an anionic protective colloid on the basis of lignin-sulfonic acid. A fast blue dyeing was obtained.

EXAMPLE 9:

Piece-goods of unmodified polypropylene fibers were padded, with a liquor-pick up of percent by weight, with an aqueous liquid at room temperature which contained per liter 20 g of the mordant dyestuff mentioned in Example 20 g of chromium (lll)- acetate-sulfate,

10 g of a 2 aqueous solution of a completely etherified locust bean flour and 2 g of the reaction of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxide and steamed, with or without intermediate drying, in the high-temperature steaming apparatus at 130C for 20 minutes. Then, the material was rinsed and soaped in the usual manner.

A fast blue dyeing was obtained.

When proceding by this method prints can also be effected on the material.

We claim:

1. A process for the single-bath dyeing or printing of unmodified polypropylene fibers with metal-complex dyestuffs, which comprises: reacting under hightemperature dyeing conditions above C on these textile materials aqueous liquors or printing pastes containing dispersed metallizable dyestuffs and compounds yielding polyvalent heavy-metal ions capable of forming color lakes in the presence of a dispersion system based upon polyglycol ethers or esters.

2. A process as recited in claim 1, wherein the components forming the metal complex dyestuff are applied to the material according to the exhaustion method for 40 to 70 minutes at a temperature from C to C.

3. A process as claimed in claim 1, wherein the components forming the metal complex dyestuff are padded or printed onto the material and these paddings or prints and then steamed, with or without intermediate drying, in a pressure steamer at 100 to 135C for 10 to 40 minutes.

4. A process as claimed in claim 1, wherein as metallizable dyestuff azo developing dyestuffs independent of their chemical constitution are used.

5. A process as claimed in claim 1, wherein as metal= lizable dyestuffs water-insoluble disperse dyestuffs in= dependent of their chemical constitution are used.

6. A process as claimed in cl ims 1, wherein as metal= lizing agent thermally relatively instable chelates of copper, nickel, cobalt, chromi m, iron. aluminum, zinc with nitriloacetates, ethylene diamine tetraacetates,

polyphosphates, tartrates, citrates, triethanol amine or with ammonia are used.

7. A process as claimed in claim 1, wherein as metallizing agent chromium (IIl)-acetato-sulfate of the formula CH COO Cr cn coo is used.

8. A process as claimed in claim 2, wherein as dispersion system for the exhaustion method anionic protective colloids having a dispersing effect based upon lignin-sulfonic acid, in combination with a non-ionic auxiliary based upon the reaction product of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxide are used.

9. A process as claimed in claim 3, wherein as dispersion system for the pad-steaming or print-steaming pro- 

1. A PROCESS FOR THE SINGLE-BATH DYEING OR PRINTING OF UNMODIFIED POLYPROPYLENE FIBERS WITH METAL-COMPLEX DYESTUFFS, WHICH COMPRISES: REACTING UNDER HIGH-TEMPERATURE DYEING CONDITIONS ABOVE 100*C ON THESE TEXTILE MATERIALS AQUEOUS LIQUORS OR PRINTING PASTES CONTAINING DISPERSED METALLIZABLE DYESTUFFS AND COMPOUNDS YIELDING POLYVALENT HEAVY-METAL IONS CAPABLE OF FORMING COLOR LAKES IN THE PRESENCE OF A DISPERSION SYSTEM BASED UPON POLYGLYCOL ETHERS OR ESTERS.
 2. A process as recited in claim 1, wherein the components forming the metal complex dyestuff are applied to the material according to the exhaustion method for 40 to 70 minutes at a temperature from 120*C to 135*C.
 3. A process as claimed in claim 1, wherein the components forming the metal complex dyestuff are padded or printed onto the material and these paddings or prints and then steamed, with or without intermediate drying, in a pressure steamer at 100* to 135*C for 10 to 40 minutes.
 4. A process as claimed in claim 1, wherein as metallizable dyestuff azo developing dyestuffs independent of their chemical constitution are used.
 5. A process as claimed in claim 1, wherein as metallizable dyestuffs water-insoluble disperse dyestuffs independent of their chemical constitution are used.
 6. A process as claimed in claims 1, wherein as metallizing agent thermally relatively instable chelates of copper, nickel, cobalt, chromium, iron, aluminum, zinc with nitriloacetates, ethylene diamine tetraacetates, polyphosphates, tartrates, citrates, triethanol amine or with ammonia are used.
 7. A process as claimed in claim 1, wherein as metallizing agent chromium (III)-acetato-sulfate of the formula
 8. A process as claimed in claim 2, wherein as dispersion system for the exhaustion method anionic protective colloids having a dispersing effect based upon lignin-sulfonic acid, in combination with a non-ionic auxiliary based upon the reaction product of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxide are used.
 9. A process as claimed in claim 3, wherein as dispersion system for the pad-steaming or print-steaming process non-ionic auxiliaries based upon the reaction product of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxide, in combination with non-ionic protective colloids having a thickening effect of the type of a completely etherified locust bean flour are used.
 10. A process as claimed in claim 1, wherein the non-ionic oxethylation products recited in claim 8 is used in the exhaustion and in the pad-steaming or print-steaming method also for accelerating the metallization of the dyestuff and thus the formation of the colour lake. 